DE2261505A1 - CELLULOUS ACTIVE DYES - Google Patents

Description

The invention relates to new cellulose reactive dyes and especially on new cellulose reactive dyes of the triphenylniethan- or xanthene series. '

It has been found that valuable cellulose reactive dyes with extremely bright hues characteristic of this range of dyes, but with one unexpected high degree of lightfastness can be produced by having a cellulose-reactive group via an amine or

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Diamine residue on a sulfonyl group in one of the phenyl nuclei in certain members of this series.

Thus, according to the invention, there are dyes of the formula

H (CH ₂ ) _n

(1)

suggested where

1 2

3 represents hydrogen or an alkyl group and R represents represents an alkyl, aryl, or substituted aryl group

1 2
or R and R together with the N atom form a 5-membered or 6-membered heterocyclic ring; , η each independently represents O or 1;

or Υ each independently represents hydrogen / a methyl group or the two Ys together represent an oxygen atom; X ~ stands for SO, or stands for CCÜ · k «nn, '* enn the two Ys stand for -0-;

Am stands for the group NH or an amine or diamine radical, wherein the SCU group is bonded to the nitrogen atom or to one of the two nitrogen atoms; and Z is a cellulose reactive group attached to a carbon or nitrogen atom in the radical Am

12th
The alkyl groups represented by R and R in Formula 1 can be any length, but it is preferred that they have up to 4 carbon atoms, such as methyl, ethyl, n-propyl and n-butyl.

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Examples of aryl or substituted aryl radicals represented by ΈΓ are in particular the radicals of the benzene series, in which the benzene ring or rings can be substituted, for example by halogen atoms such as F, Cl or Br, or by CF, or NO ₂ .

Examples of groups reactive with cellulose, represented by Z. are aliphatic sulfonic groups that are one Contain sulfate ester group in the ß-position to the sulfur atom, for example the ß-sulfatoethylsulfon group., α, β-unsaturated Acyl radicals of aliphatic carboxylic acids, for example acrylic acid, δ-chloroacrylic acid, propiolic acid, maleic acid and mono- and dichloromaleic acid as well as the acyl radicals of these named acids, which contain a substituent, which reacts with cellulose or polyamides in the presence of an alkali, for example the radical of a halogenated aliphatic Acids such as chloroacetic acid, ß-chloro and ß-propionic acid and <x »ß-dichloro and -dibromopropionic acid. Other examples of groups reactive with cellulose or polyamides are tetrafluorocyclobutane carbonyl, trifluorocyclobutene carbonyl, Tetrafluorocyclobutylethenylcarbonyl, irifluorocyclobuteneethylcarbonyl and heterocyclic radicals which contain 2 or 3 nitrogen atoms in the heterocyclic ring and at least a cellulose reactive substituent on a carbon atom included in the ring.

Examples of such heterocyclic radicals are:

2,3-dichloro-quinoxaline-5- or -6-sulfonyl, 2,3-dichloro-quinoxaline-5- or -6-carbonyl, 2,4-dichloro-quinazoline-6- or -7-sulfonyl, 2,4 ■, 6-TrichloΓO-quinazoline-7- or -8-sulfonyl, 2,4,7- or 2,4,8-trichloro-quinazoline-6-sulfonyl, 2, ^ - dichloro-quinazoline-e-carbonyl, 1, ^ - Dichldro-phthalazin-Grcarbonyl, -

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4,5-dichloro-pyridaz-6-on-1-yl, 2,4-2ifluoro - ^ - chloro-pyrimid-e-yl, 2,4-dichloro-pyrimidine-5-carbonyl, 2-methyl-sulfonyl-5-chloro-6-methyl-pyrimid-4-yl, 4 (4,5-dichloro-pyridaz-6-on-'1-yl) benzoyl, 4 (4, $ - dichloro-pyridaz-6-on-1-yl) phenylsulfonyl and particularly

s-triazin-2-yl and pyrimidin-2-yl or 4-yl radicals,

those in at least one of the remaining 2r, 4 and 6 positions folö · »* ·» contain: a bromine or preferably a chlorine atom, a sulfonic acid group, a thiocyanato group or an aryloxy or arylthio group with an electronegative Substituents such as sulfophenoxy, sulfophenylthio, nitrosulf ophenoxy, disulfophenoxy and sulfonaphthoxy; or one Group of formula

1
wherein Y stands for a group which is necessary for the formation of a 5- or 6-membered heterocyclic ring, which can carry substituents or form part of a condensed ring system; or a quaternary ammonium group such as a pyridinium group; or a group of the formula

3 4
where R ^ and R each represent the same or different alkyl,

Cycloalkyl, aryl or aralkyl groups or R ^ and Ii ^ together with the nitrogen atom form a 5- or 6-membered one

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heterocyclic ring "; or a group of

formula

KR ⁵ - S - C ^ ' ik)

where Έ? and R may be the same or different and each represent a hydrogen atom or an alkyl, aryl or aralkyl group. ■ - -

In the case where the pyrimidine ring or the iriazine ring carries only one such reactive substituent, the ring can also have a non-reactive substituent on the contain remaining carbon atoms.

Kit the term "non-reactive" ■ Substituent is a group meant by a covalent bond to a carbon atom of the triazine or pyrimidine nucleus is bound, the covalent bond is not broken under the conditions that are used to apply the reactive dye.

Examples of such substituents are primary. Amino and hydroxyl groups as well as mono- or disubstituted amino groups, etherified hydroxyl groups and etherified mercapto groups. In the case of substituted amino groups, this class includes, for example mono- and dialkylamino, wherein the alkyl groups preferably contain at most 4 carbon atoms and may also have substituents such as hydroxyl and _alkoxy} and phenylamino and naphthylamino groups which contain preferably SuIfqnsäuresubstituenten. In the case of etherified hydroxyl and mercapto groups, the class includes, for example, alkoxy and alkylthio groups, preferably those of low molecular weight, ie. those that contain up to 4 carbon atoms, and also

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Phenoxy, phenylthio, naphthoxy or naphthylthio groups. Specific examples of each of these classes are as follows:

Pie thy I amino-,

ethylamino,

Dimethylamine,

3-hydroxyethylamino,

Di- (fi-hydroxyethyl) -amino-,

ß-chloroethylamino,

Cyclohexylamine-,

ι '

Anilino,

Sulfophenylamino,

Disulfophenylamino,

N-Kethylsulfophenylamino-,

N-ß-Hydroxyäthy1su1fophenylamino- _t mono-, di- and trisulfonaphthylamino-, SuIfo-o-tolylamino-,

Carboxyphenylamino and sulfocarboxyphenylaisino, Ν-ω-sulfomethylphenylamino-,

? iethoxy, ethoxy and butoxy,

Phenoxy, methylphenoxy and chlorophenoxy as well Phenylthio groups.

Chlorine atoms or cyano, nitro, carboxy and carbalkoxy groups in the 5-position of a pyrimidyl radical also fall into the Class of non-reactive substituents.

Alternatively, the second substituent can be on a chloro-s-triazine group be a radical that carries another group reactive with cellulose, such as an anilino or naphthylamino group, which carries a ß-Sulfatoäthylsulfonylgruppe, the is bonded to a carbon atom of the ring, but in particular the radical of a diamine which is a mono- or dichloro-striazine group bonded to the second nitrogen atom, that is a group of the formula

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C <1 - ^c CH

Μ I I / ■ C5>

1 '

ci ⁰¹

wherein Q stands for the N ₁ N ¹ divalent radical of an aliphatic, aromatic or heterocyclic diamine and R stands for Cl or an amino, substituted amino or etherified hydroxyl group.

Examples of radicals represented by Q are ΙΤ, ϊϊ'-piperazinylene and radicals of the formula

- N - Q ¹ - N - "

7 fi ■

where R 'and S are independently hydrogen or an alkyl or hydroxyalkyl group with up to 4 carbon atoms, such as diethyl, iLthyl, β-hydroxyethyl, n-propyl, n-eutyl and γ-hydroxypropyl, and Q is an aliphatic or aromatic Radical, ie for example an alkylene, poly (alkyleneimine) or dialkyloxide radical, such as ethylene, propylene, tri-, tetra- and hexamethylene, -C ₂ H ^ NEC ₂ H ₄ -, -C ₂ H ₄ CKHC ₂ H _{4) 2} - and C ₂ K preferably ₄ OC or a divalent radical of the benzene or naphthalene series which contains one or two Sulfpnsäuregruppen, such as a mono- or Disulfophenylen- or Disulfonaphthylen radical, or a divalent radical of stilbene, diphenyl -, diphenylmethane, diphenylurea, diphenoxyethane or diphenylamine series, which preferably contains 1 or 2 sulfonic acid groups.

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A special class of new dyes are these in which the reactive group assumes the formula (5), where the radical R is a second triphenylmethane or xanthene radical bound by a -SGpAm radical as in Fornel (1) is.

For example, the symbol Am can represent an aniline radical, where Z is bonded to one of the carbon atoms of the benzene ring. Preferably, however, Am provides the Radical of any aliphatic, aromatic or heterocyclic Diamine, in which an acylatable hydrogen tor. is present on each nitrogen atom referred to above with the symbol Q, the type discussed.

The invention also relates to a method of manufacture new dyes, which is carried out by dal: nan a compound of the formula

(6)

wherein the symbols R, R, X ~, Y and η have the above given ■

Have meanings and Am stands for -NH- or the radical of a diamine, with an anhydride or with a halide an acid, of which the acid radical bears a substituent which leads to a chemical reaction under formation; one

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chemical bond with the Paser, or with a heterocyclic compound which has a halogen atom on a carbon atom of the heterocyclic nucleus and also a contains reactive substituents of the type just explained. -

The above method can be carried out by that one stirs a mixture of the reactants in an aqueous medium at a suitable temperature conveniently, -which from ⁰ ° C in the case of cyanuric chloride to 5O ⁰ C or higher in the case of less reactive acyl halides , Anhydrides or heterocyclic compounds. As a general rule, it is preferred to add an acid scavenger during the course of the reaction to keep the pH within the 5-8 limits. .

The compounds of formula (6) used in the above process can generally be obtained by using a compound of the formula

(7)

produced by processes known per se, this into the sulfon chloride and the latter is reacted with ammonia or 1 mole of a diamine of the formula H- (Am) -H. Examples of the latter are the following:

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Piperazine,

aliphatic diamines such as alkylenediamines and other aliphatic α »ω-diamino compounds, such as ζ.ΐ Ethylenediamine,

1,2- and 1,3-propylenediamine, 1,6-hexylenediamine, ■ - ■ ..

Diethylenetriamine,
Triethylenetetramine,
Di- (ß ^ aminoethyl) -ether,

aromatic diamines of the benzene and naphthalene series, and especially those containing 1 or 2 ßCUH groups, such as 3:
in- and p-phenylenediamine,

1,5-phenylenediamine-A-sulfonic and -4,6-disulfonic acid, 1 ^ -phenylenediamine-4-sulfonic and -2,5-disulfonic acid, 2,6-naphthylenediamine-4-sulfonic and 4-, 8 -disulfonic acid, 1,5-naphthylenedialin-2- and -4-sulfonic acid and -3,7-disulfonic acid,

4,4'-diaminodiphenyl-2-sulfonic and * 5,2'-disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4,4 ^I -diaminodiphenylurea-2,2 ^I - and -3, 3'-disulfonic acid,

4,4'-diaminodiphenylamine-2,2'-disulfonic acid, 4,4'-diaminodiphenoxyethane-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane-2,2'-disulfonic acid, 4.4 ^l -diaminoazobenzene-2 -sulfonic and -2,2'-disulfonic acid,

N-ethyl- and N-ethyl-1,4-phenylenediamine-2-sulfonic acid and
li (ß-hydroxyethyl) ethylenediamine.

Examples of halides or anhydrides of acids or heterocyclic compounds that can be used are carbyl sulfate and the anhydrides or acid halides of a. _} B- unsaturated aliphatic acids, such as chloromaleine

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acid anhydride, propiolyl chloride and acryloyl chloride, the acid chlorides of halogenated aliphatic acids, e.g. chloroacetyl chloride,
Sulfochloroacetyl chloride,
ß-bromo- and ß-chloro-propionyl chloride, &, ß-dichloro- and -dibromo-propionyl chloride, 2,2,313-tetrafluorocyclobutane-carbonyl chloride, ß- (2,2,3,3-tetrafluorocyclobutyl) -acryloyl chloride, 2,3 , 3-Trifluorocyclobut-i-en-carbonyl chloride, ß- (2,3 ί3-Trifluorocyclobut-1-enyl) -acrylylchlorid, as well as heterocyclic compounds that contain at least 2 nitrogen fat ones in the heterocyclic rings and the 2 or more halogen atoms , in particular chlorine atoms, in the ortho-position to the nitrogen disruptive entablten, vie _χ ζ.Β.

g ^ -Dichloro-quinoxaline - ^ - and -6-carbonyl chloride, 2,3-dichloroquinoxaline-5- and -6-sul-phonyl chloride, 2,4-dichloroquinazoline-6- and -7-sulfonyl chloride, 2,4,6-trichloroquinazoline-7- and -8-sulfonyl chloride, 2,4,7- and 2,4,8-trichloroquinazoline-6-sulfonyl chloride, 2,4-dichloroquinazoline-e-carbonyl chloride, 1, ^ - dichloro-phthalazine-G-carbonyl chloride, 2,4-dichloro-pyrimidine-5-carbonyl chloride, ß- (4,5-dichloropyridazonyl-1) propionyl chloride, 1- (4'-chloroformylphenyl) -4,5-dichloro-6-pyridaz on, 1- (4'-Chloro sulfonylphenyl) -4,5 ~ dlchlorq-6-pyridaζon, 2,4,6-tribromo- and -trichloro-pyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,4,5,6-tetrachloropyrimidine,

2-Kethylsulfonyl-4,5-dichloro-6-methylpyrimidine, 5- ^ methyl-2,4,6-trichloropyrimidine, 5-nitro-2,4,6-trichloropyrimidine, 2,4-dichloro-5-nitro-6-methylpyritαidine, 2,4-dichloro-5-ni ■ fcΓopyriIrlidin, 2,4,6-trichloro-5-cyanopyrimidine,

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^ -Athoxycarbonyl ^^ - dichloropyrimidine, 2,4 - dichloropyrimidine-5-carbonyl chloride, Cyanuric bromide, cyanuric chloride

and also the primary condensation products of cyanuric chloride or cyanuric chloride with ammonia, an alkali metal sulfite cd er thiocyanate or an organic mercaptan, or an organic hydroxy compound or an organic primary or secondary amine, e.g.

Methanol, ethanol,

Isopropanol, phenol,

o-, m- and p-chlorophenol, o-, m- and p-cresol, o-, m- and p-sulfophenol, Thiophenol, thioglycolic acid, dimethyldithiocarbamic acid, Mercaptobenzthia zol, thioacetamide,

Methyl, dimethyl, ethyl, diethyl, n-propyl,

Isopropyl, butyl, hexyl and cyclohexylamine, toluidine, piperidine, korpholine, kethcxyethylamine, ethanolamine, aiinoacetic acid, aniline-2, ^/ i -, - 2,5- and -5,5-disulfonic acid, grthanilic acid, metanilic acid, 3ulfanilic acid , 2-, 1- and 4-aminobenzoic acid, ¹ T- and 5-3ulf o-2-a ™ inobenzoic acid, 4- and 5-3ulfo-o-toluidine,

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5> -amino-2-hydroxybenzoic acid, 2-amino-ethanesulfonic acid, Aminonaphthalene iono- and disulfonic acid and ST-kethylaininoethanesulfonic acid;

as well as the secondary condensation products of cyanuric chloride with

Alkali metal sulfites !!, alkali metal thiocyanates, Phenols and thiophenols

which contain an electronegative substituent and Connections of the formulas

H - S - c "V ■. <8>

Il </

H-S-C-K (9)

H - S - C. * - (10)

rin Y ¹ , H ^, R ⁴ , R ^? and R ^{6 has} the meanings given above

vjo
own.

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L \ iT ■ Introduction of a reactive group of the kind described by the formula (5), the compound der'Formel (6) can be reacted with a l \ ^T , ir-3is- (chloro-s-triazinyl) diamine, in which at least one of the chloro-s-triazine groups contains 2 chlorine atoms, such as z.3. the reaction product of one of the above-mentioned diamines with 2 grains of cyanuric chloride or with a NoI cyanuric chloride and a KoI. the primary condensation product of cyanuric chloride and ammonia, a primary or secondary amine, or an alcohol or phenol as discussed above. When reacting a bis (dichloro-s-triazinyl) diemine, the formula of the final dye will depend on the ratios used in the reaction. If equimolar amounts are used, the dye contains a single triplienylmethane or xanthene radical and a reactive group of the formula (5) in which R is a chlorine atom. If, on the other hand, 2 holes of the compound of the formula (6) are used for each 1 hole of the Bl3 ~ (dichloro-striazinyl) diamine, the dye obtained contains 2 triphenylmethane or xanthene radicals, which are replaced by the bis (chloro-s-triazinyl) diamine residue are linked to one another. - '

The invention also provides a method of manufacture of the new dyes according to the invention wherein Ao for the Radical of an amine or diaoin, which thereby is carried out that one is a compound of the formula

H (CH

(CH_) H 2 n

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(11)

with an AnIn or diamine of the formula

H-Am-Z (12)

Ί 2 implements, where the symbols H, R, X, Y, Z, Am and η die

Have the meanings given above.

The above method can be carried out by that, the mixture is stirred a mixture of the reactants in an aqueous medium, preferably at a temperature of 10 to 4O ⁰ G, and preferably also at a pH of 5 to 7 x conveniently

The compounds of the formula (11) can generally be obtained by processing a compound of the formula (7) processes known per se and then into the Sulphonic chloride transferred.

Examples of compounds of the formula (12) are: 3- or 4-ß-sulfatoethylsulfonylaniline, 4-methyl-3-ß-sulfatoethylsulfonylaniline, 2-methoxy-5-ß-sulfatoethylsulfonylaniline.und

the monocondensation products of diamines and halides or anhydrides of acids or heterocyclic compounds,

which are explained above.

The dyes of formula (1) wherein die.mit cellulose reactive group Z is a s-triazine nucleus by a chlorine or Br omatom and a> · amino or substituted amino group is substitutable, tuiert, krmen also obtained by that a cellulose-reactive dye of the formula (1), in which Z is a DIchloro- or dibromo-s-triazine group, is reacted with ammonia or an amine.

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The cellulose-reactive dyes of the formula (1) in which the cellulose-reactive group is an s-triazine nucleus which is substituted by SC ₃ -H, a quaternary ammonium group or a group of the formula (2), (3) and (4) is, can be obtained by a cellulose-reactive dye of the formula (1) which contains an s-triazine group which is substituted by at least one chlorine or 3romatom, with an alkali metal salt of sulfurous acid, a tertiary amine or a _encryption> compound of the formulas (S), (9) and (10) are reacted.

The reactions may also be v run / earth, and the mixture is stirred can the Reaktionsteilnehner together in an aqueous medium at a suitable temperature which is generally in the range of 30 to 95 ⁰ C, and the pE by addition of an acid-binding agent to an appropriate value holds. In the case where ammonia or an amine is the reactant, an excess can be used, this then acting as an acid-binding shaker. Otherwise, sodium carbonate or sodium hydroxide can be conveniently used as an acid-binding agent.

The new dyes can be used to dye a wide variety of textile materials, such as natural ones Proteins, for example whole, silk and leather, super polyamides and in particular natural or regenerated Cellulosic textile materials such as cotton, linen, and viscose rayon. For dyeing cellulose materials the dyes are preferably by printing or dyeing in conjunction with treatment with a acid-binding agents used, such as caustic soda, sodium carbonate, sodium triphosphate or sodium silicate, which can be applied to the textile material before, during or after the application of the dye. If the

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in this way applied new dyes old the SeIIu. react loosely, then they result in bright yellowish red to bluish red! Wash and with a surprisingly high degree of fastness to light. In addition, many of the new dyes produce hues that fluoresce when exposed to UV light will. This property can be beneficial in manufacturing be exploited by multi-colored materials, such as by the usual 'textile printing processes using cellulose reactive dyes can be used, or by the more recent processes, in which several reactive dyes in streams on one running Textile fabric can be applied to produce a pattern, as described, for example, in G3-P3 1 243 403 is. The dyes can, for example, be used together with fluorescent brighteners of high substantivity can be used to expand the range of hues obtained under the influence of UV light.

The invention is illustrated in more detail by the following examples, wherein the parts are by weight.

example 1

5 parts of the anhydrous dye CI Acid Red 52 are added to SO parts of chlorosulphonic acid at such a rate that the temperature does not rise above 1G ° C. ■ The solution is then heated to 70 ^C C and stirred for 17 st, then cooled and poured into 450 Poured parts of ice and 150 parts of water. The precipitate is quickly filtered off, washed quickly with 1C0 parts of ice-cold water and added to a solution of 5 parts of N-ß-hydroxyethylethylenediamine in IOC parts of water. The mixture is at pH 9 to 1C

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Stirred for 2 st at room temperature, and then the solid The product is filtered off and washed with 50 parts of ice-cold water.

2 parts of cyanuric chloride are dissolved in 10 parts of warm acetone and the solution is added to a stirred mixture of 50 parts of ice, 50 parts of water and 1 part of dispersant. A solution of 1.7 parts of metanilic acid in 5C parts of water with 0 to 5 ^C and a pH of 6 to 7 are added to the suspension, and the mixture is then 1/2 st at pH 6 to 7 and at 0 to 5 ° C stirred. The Genisch is filtered off, the product of paragraph 1, is added to the filtrate, and the mixture is 1 st 1/2 at pH 9 and stirred at 35 ° C to 40 ⁰ C ". Salt is added so that a concentration of 100 g / l is formed, and the precipitate is filtered off and dried.

The product contains 1.1 atoms of hydrolyzable chlorine per mole of dye. When it is shared with cellulose fibers an acid binding agent is applied, then it dyes fibers in bright bluish red shades with a good wash fastness.

Example 2

If the 5 parts of N-ß-Hydroxyäthyläthylendiaoin from Example 1 replaced by 10 parts of 60; iiigem aqueous ethylenediaain, then the dye obtained dyes cellulose fibers in bright bluish red shades with similar fastness properties.

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Example 3

5 parts of anhydrous CI Acid Red 52 are converted into the sulfonyl chloride as in Example 1. The isolated paste is quickly added to a solution of 4.5 parts of 1,4-Fhenylendiamin-2-sulfonic acid in 150 parts of water at pH 7 and at 20 ^c C. The mixture is stirred at room temperature and at pH 6-7 for 2 hours, a clear solution being obtained. Salt is then added so that a concentration of 15c g / l is obtained and the precipitate is then filtered off. The filter cake is dissolved in 10 parts of V = sser with pH 6 to 7, 'and the solution is ^{cooled to 0 to 5 ° C 3} ^ - and made into a suspension of 3 parts of cyanuric chloride, 50 parts of water, 50 parts of ice and 1 part Dispersant added. The mixture is stirred for 1 hour at 0 to 5 ^° C. and pH 6 bis, then filtered and 2 parts of potassium dihydrogen phosphate and 1 part of disodium hydrogen phosphate are added, before sufficient salt is added so that a concentration of 200 g / l is obtained. The precipitate is filtered off, made into a paste with 1 part of potassium dihydrogen phosphate and dried in vacuo at room temperature. The product contains 2 atoms of hydrolyzable chlorine per mole of dye. When the dye is applied to cellulose fibers together with an acid-binding smock, it dyes the fibers in bright reddish mauve shades with good washfastness.

Example 4

Venn the 1,4-phenylenediamine-2-sulfonic acid of Example 3 by an equal amount of 1,3-phenylenediamine-4-sulfonic acid is replaced, then a dye with a similar hue and with similar fastness properties is obtained.

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example 5

10 parts of anhydrous CI Acid Red 52 are converted into the sulfonyl chloride as in Example 1. The isolated paste is quickly added to 100 parts of cold ammonia solution (density 0.38), and the mixture is stirred for 2 hours at room temperature. The sulfonamide is precipitated by acidification to pH 7 sit concentrated hydrochloric acid (36 ° Tw), and then filtered and finally suspended in a Genisch of 40 parts of acetone, 100 parts of water and 1 part of wetting agent at 0 to 5 ^C C and pH 10, to 11 and stirred vigorously, during which a solution of 5 parts of cyanuric chloride in 30 parts of acetone is added over the course of 1 hour, the pH being kept at IC to "1 during the addition and another 1/2 hour by the occasional addition of 2N sodium carbonate solution and the temperature is maintained by external cooling at C to 5 ° C. The pH is then adjusted to 6 to 7 by the dropwise addition of 2N hydrochloric acid, and the dye is isolated by filtration, washed with 20 parts of ice-cold water and im It contains 1.8 atoms of hydrolyzable chlorine per KoI dye and dyes cellulose fibers in reddish blue shades in the presence of an acidic binder.

The following table gives examples of dyes, at denon the sulfonyl chloride from CI Acid ßed 52 with a Overshoe of the diamine is condensed in column II and the product thus obtained with that described in column III Acylating agent is acylated.

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SAD CWIQJNAL

ο to co

E.g. II III Hue on
cellulose 6th 4-, 4'-diainino-diphenyl ether-3,3'-disulfonic acid Cyanuric chloride bluish-red 7th A, 4'- ^{diaminostilbene-2,2 1} -disulfonic acid ! I Il 8th 4,4'-diaminodiphenyl-2,2'-disulfonic acid It It 9 A, 4'-diamino-3,3'-dimethyldiphenyl-2,2'-disul-
fonic acid Il Il 10 4 ^ 4 <■ _Dinino-3 _r 3 '-dime thoxydiphenyl-2,2' -
diculfonsaupe Il violet

Example 11

10 parts of the anhydrous dye CI Acid Hed $ C are converted into the sulfonyl chloride in the same way as is described for CI Acid Red 52 in Example 1. The isolated fast is quickly added to a stirred solution of 1.6 parts of 2,5-diaminobenzenesulfonic acid in 8CC parts of water, and the mixture is stirred for 18 hours at seam temperature and pH 6 to 7, a clear solution being obtained 200 parts of sodium chloride are then added, and the product is isolated by filtration, it is then dissolved in 2CO parts of water, 5C parts of Sis and 1 part of dispersant, and a 1 part solution is added to the solution which is stirred ^{at 0 to 5 ° C} Cyanuric chloride in 1C parts of acetone is added, the suspension is ^{stirred for 2 hours at 0 to 5 °} C. and at a pH of 6.5 and filtered, and the product is isolated by adding sodium chloride. The product is isolated by filtration , intimately mixed with 0.4 parts of potassium dihydrogen orthophosphate and 0.2 parts of disodium hydrogen orthophosphate and dried in vacuo at room temperature. Analysis of the dye shows that it contains 2.2 parts of hydrolyzable chlorine per column of dye holds. If it is applied to cellulose fibers together with an acid-binding agent, then the fibers are dyed in bright pink shades with good washfastness.

In the examples in the table below, the sulfonyl chloride of CI Acid Red 50 is condensed with an excess of the diamine from Column II and the product becomes then acylated with the acylating agent from column III.

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σ co oo

E.g. II 12th Ethylenediamine 13th 2,5 dinminobenzene
sulforic acid 14th N-ß-hydroxyethyl
ethylenediamine 15th 2,4-diaminobenzene
sulfonic acid 16 2,5-diaminobenzene
sulfonic acid 17th Il 18th II 19th Il 20th Il 21 It 22nd Il 23 It 24 It

III

2,4-dichloro-6- (3'-sulfpphenylamino) -u-triazine 2,4-dichloro-6-amino-ß- ~ triazine

2,4-dichloro-6- (3'-sulfoph.enylamino) -s-triazine

2,4-dichloro-6- (2 '^' - disulfophenylamino) -triazine

2,4-dichloro-6- (5'-sulfonaphth-2'-ylamino) -striazine

2,4-dichloro-6- (N - & / - 3ulfomethylanilino) -s-triazine

2,4,6-trichloropyrimidine

2,4,5,6-tetrachloropyrimidine

5-cyano-2,4,5-trichloropyrimidine

2,3-I> ichloΓoquinoxaline-6-caΓbonylchloride

4,5-dichloro-6-methyl-2-methylsulfonylpyrimidine

β- (4 _t 5-dichloropyridaz-3-onyl-'1) propionyl chloride

3, & - Dichloro.pyT ^% idazine-4-carbonyl chloride

2,4-dichloropyrirnidine-5-sulfonyl chloride

Hue on
cellulose

pink

VM I

IS »

ro

CD

E.g. II III Color
Line 26th 2,5 kifirainobenzene
sulfonic acid 2-chlorobenzothiazole-6-carbonylchloride pink 27 Il 2,4,6-trifluoro-5-chloropyrimidine Il 28 It β- (2,2,3,3-tetrafluorocyclobutyl) acryloyl chloride It 29 It Carbyl sulfate It 30th ti 2,4-dichloro-6- [v - (2 "-chloro-4" -amino-s-triazine-
6 "-ylamino) -4'-sulfophenylamino] -s-triazine fl 31 Il 2,4-dichloro-6-L4 '- (2 "-chloro-4" -m-sulfophenyl-
amino-s-triazine-6 "-ylamino) -3'-sulfophenylamineq] -
s-triazine Il 32 Il 2,5-bis- (2 ', 4'-dichloro-s-triazine-G'-ylamino) -
benzene-1,4-disulfonic acid (1 mol) If 33 Il 4,4'-bis (2 ", 4" -dichloro-fi-triazin-6 "~ ylamino) -
stilbene-2,2'-diGUlfonG acid (0.5 mol) It 34 Il 2,4-dichloropyrimidine-5-carbonyl chloride It 35 ·· ß-Chloroäthylsulfnnj'l-endomethylene-cyclohexime-
carbonic acid chlorine! egg ti 36 fl 2,4-dichloro-G- (4'-sulfophenylamino) -s-triazine Il

E.g. II III , Hue on
Cellulose. 37 2,5'-Maminobenzene-
sulfonic acid 2,4-dichloro-6- (2'-methyl-5'-sulfophenyl-
araino) -s-triazine pink 38 It 2 _t 4-dichloro-6- (2'-carboxy-4'-sulfophenyl-
amino) -s-triazine Il 39 π 2,4-DiChIOrO-O- (4 '-sulfoplienoxy) -s-triazine Il 40 It 2,4-dichloro-6-methoxy-s-triazine Il 41 Il 2,4-dichloro-6- (6'-sulfonaphth-2'-ylainino) -s-
triazine Il 42 2,4-dichloro-6- (5 ', 7'-disulfonaphth-2'-yl- ·
amin.o) -s-triazine ti 43 Il 2,4-dichloro-6- (3 ', 6', 8'-trisulfonaphth-1'-
ylaniino) -s-triazine It

Example 44

The replacement of CI Acid Red 52 in Example 1 by a, equivalent weight of the acidic dye 3 * 6-Bis-N, N-dir.ethylaaino-9- (2 ' , 4'-disulfophenyl) xanthene produces a dye by means of similar combinations, which when applied on cellulose in the presence of an acid-binding coat the fibers in bright bluish red tones with good Color fastness.

In the following table further examples are given in which the compounds of the formula (13) , wherein the

13th
Groups 3 to R correspond to those in column II, converted into the honosulfonyl chloride and then reacted with 1 mol of the dianiine in column III and the product is acylated with the agent from column IV »

(13)

309826/1069

E.g.

46

Ca) O to OO

47

4R

50

II

= H

Ro 2

CH ₅ CH ₂ R ^ ⁼ H

= H = CH ₃ ^ R ² R ₂ - E ₁ , - H -CH ₂ CHpCH ₂ CH ^E 3 -CHpCHpCH ₂ CH ₂

I ₇ = II

i _v R ₂ = U = II

CH ₂ CHpOCH ₂ CH ₂ -

III

P. , i3-diaminobenzenesulfonic acid

IV

2,4-l) ichloro-6-m-sulfophenyl-amino-s-triazine

Color based on cellulose

bluish-red

yellowish red

bluish-red

Red

E.g. :
i II III I. IV 51 R ₀ = 4-nitrophenyl
R ₁ = R-, = II 2,5-diarainobensol-
suifonsüure i?, 4-DichloiO-6-m-nulfo-
phenyl-amino-G-triazine 52 Rp = 3-nitrophenyl Il It R ₁ = Rj = II 55 R ₀ = 4-chlorophenyl Il It approx
ο R ₁ - R ₅ = II co
OO 54 Rp = 4-bromophenyl Il ti 26 / R ₁ = R ₅ = H 1069 55 R ₀ = 4-trifluoro
methylphenyl It ti R ₁ - R ₅ = H 56 R ₀ = 3,5-dichlorophenyl H Il
Pi ■ - ^: \ R ₁ = R ₅ = H;

Shade nuf
Cellulose

violet

Example 57

IC parts of the anhydrous dye CI Acid Blue 1 v, '© rä, §; sin similarly - as in Example 1 converted into the .Mono sulfonyl chloride. The paste obtained in this way is added to a solution of 5 parts of Λ , 4-phenylenedias; in-2-sulfos, acid in 6C parts of water, and the mixture is stirred at home temperature and at pH 6 to 7 a 'clear solution has emerged. Then 175 parts of sodium chloride are added, and the precipitate is filtered off and redissolved in 2CO parts of water. The solution is cooled to 5 ° C, and then 50 parts of ice and 1 βΐί dispersant are added. Then a solution of 2 parts of cyanuric chloride is added in 10 parts of acetone, and the Genisch is then stirred at 0 to 5 ⁰ C and a pH of 6 to 2 and st long. filtered, and the dye is isolated by salting out with sodium chloride 25%. The product 'domestic product is isolated by filtration, ilaliumdihydrogenorthophiisphat intimately 1 -part and O ₁ 5 parts of disodium

hydrogen orthophosphate mixed and dried in a vacuum » When applied to cellulose fibers in connection with cit. The dye stains the fibers with an acid-binding agent in bright greenish blue shades that are washable.

5eisr> lel 53 ■. ■

Instead of the 10 parts of CI-Acid Blue 1 from Example 57, an equivalent amount of the dye is used which is obtained by the condensation of 3enzaldehyde-2, 4-disulfonic acid and Ii, IJ-diethyl-m-toluidine and subsequent oxidation of the leuco ^: intermediate derivative A dye with a similar hue and with similar properties is obtained.

309828/1 © Si BAD

EXAMPLE 5 9

Instead of the 10 parts of CI Acid Blue 1 from Example 57 is used an equivalent kenge of the dye used, the "by Condensation of benzaldehyde - ^, 4 ~ & isulfanoic acid and "2» N · ' Ethylaisin ~ i, 4-xylene and subsequent "oxidation of the leuco intermediate derivative is obtained. Sa becomes a dye / cit a similar shade and properties obtain.

Example 60

A solution of 1.6 parts of p-aminobenzoic acid in 50 parts of water is added to a solution of 8.0 parts of the dichlorotria.siny compound from Example 3 in 2CO parts of water. The mixture is stirred for 4 st at 33 ⁰ C to 4C, wherein the pH is maintained by occasional simultaneous addition of 2n! Tatriuncarbonatlösung 6 to 7th The dye is precipitated by adding sodium chloride, filtered off and dried.

When applied to cellulosic fabrics in the presence of an acid-binding gown, it gives
bright bluish mauve tones with good fastness to washing.

Instead of the p-aminobenzoic acid used above, a equivalent Xenge of any of the following products can be used:

N-ifethylnetanilic acid Example 61

m-aminobenzoic acid "62

2-raphthylanine-4,8-disulfonic acid "63

Aniline-3,5-disulfonic acid "64

2-acinotoluene-5-sulfonic acid "65

3-3-3ulfatoethylsulfonylaniline "66

309826/1069

4-S-3ulfatoethylsulfonylaniline Example 67

Phenol "'" 68

whereby dyes with similar hues are obtained. They produce good authenticity on cellulose textiles versus ITass treatments.

Examples 60 to 68 inclusive also know alternatively be carried out by converting the cyanuric chloride of Example 3 through the primary condensation product of cyanuric chloride and the corresponding compound in the table above, the reaction being carried out at 45 ° C, until 1-Kol HCl has been released. In a similar way Thus, Examples 1 to 59 can be obtained by a method similar to "" in Example 60, i.e., by conversion of the corresponding compound of the formula (6) with cyanuric chloride and subsequent reaction of the product with ammonia or the corresponding amine. It will be based on the following Examples referenced:

For example, Amin

1 ketanilic acid

2 "

13 ■ '^; ammonia

14th Metanilic acid

15 aniline-2,5-disulfonic acid

16 2-naphthylamine-7-sulfonic acid

17 - Aniline-N-ij-methane-sulfonate

32 2,4-dichloro-6- (4 ^I -amino-2 ^f , 5'-

disulfoanilino) -s-triazine

36. SuIfanilic acid

37 ^ aminotoluene ^ sulfonic acid

38 2-Amino-5-5ulfobenzoic acid

39 Phenol-4-sulfonic acid

41 2-naphthylamine-6-sulfonic acid

30 9 8 26/106 9

Example A j, in

42. '2-I \ ^T aphthylamine ~ 5,7-disulphonic acid

43 1-naphthylamine-3,6,8-trisulfonic acid 44-56 metanilic acid

Further examples are given in the table below. The compounds of the formula (13)> which are those given. Meanings for R ^, Ro and R, are in the Konosulfo nyl chloride overfilled and with 1 mole of the diamine from column III reacted and acylated with cyanuric chloride, whereupon the Product condensed with the compound from column IV will.

309826/1069

C *> O CO 00 K> CJJ

cn CO

E.g. II III IV Hue on
cellulose 69 R ₁ = CH ₅ GH ₂
R ₂ - CH ₅ 1, / + - phenyl endi oral n-
2-sulfonic acid Metanilic acid bright
bluish-red R, = H
P. 70 It Il Sulfanilic acid Il 7-1 Il 1,3-phenylenediamine
4-sulfonic acid 2-aminotoluene-4—
sulfonic acid Il 72 Il Il 5-3ulfoanthranil-
acid Il 73 Il M. ammonia Il

Ul VX

σ> cn cn

Example 74

A solution of 8.5 parts of the dye which has been prepared in Example 1 in 2CO parts of water is stirred at 6C °. 1 part pyridine and 2 parts sodium sulfate are added to this solution, and the solution is then ^{stirred at 6C 0} C until the chlorine atoms have been replaced by SO, H, which is estimated by the release of sodium chloride. The dye is precipitated by adding sodium chloride and dried. When applied to cellulose, it gives bright bluish-red shades that are washable.

In place of the dye of Example 1 above, an equivalent kenge of any one of dyes 11 to 1 $ can be used. When they are applied to cellulose, then they yield pink shades with very good fastness to washing.

Example 75

A solution of 2.6 parts of aniline-3,5-dlsulfonic acid in 50 parts of water is added to a solution of the dichlorotriaζinyl compound prepared in Example 3 in 200 parts of water. The mixture is st at 35 to 40 ⁰ C for 4 wherein the pH is maintained by occasional addition of 2N Hatriumcarbonatlösung 6 to 7th The product is isolated by adding sodium chloride, collected by filtration and redissolved in 200 parts of water at 2 ° C. with stirring. A solution of 2 parts of trinethylaain in 5 parts of water is then added and the mixture is stirred for 30 minutes. The pH of the mixture is then adjusted to 7 ° C. by the dropwise addition of hydrochloric acid (36 ° Tw), and the dye is then precipitated by the addition of sodium chloride. The precipitate is filtered off and dried at 2O ⁰ C.

309826/106 9

If the dye is applied to cellulose materials together with an acid-binding gown, then it results in bright mauve tones *

Example 76

Replacement of the trimethylamine of Example 75 with an equivalent I-ienge ^, 4-Siazabicyclop ^^ octane gives a Dye with similar properties and shade.

Example 77

Replacement of the trimethylamine in Example 75 with an equivalent Kenge fyridine and heat the solution to 85 ° C up to end the quaternization, what through that in freedom set chloride ion is determined, results in a color tone, which on cellulose bluish mauve tones with good Results in fastness properties.

Example 78

When Example 77 used nicotinic acid in place of pyridine then a similar product will be obtained.

"Example 79

6 parts of anhydrous CI Acid Red 52 are as in Example 1 converted into the sulfonyl chloride. The isolated paste will quickly to a stirred solution of 4 parts of 4-ß-sulfatoethylsulfonylaniline in 300 parts of water and 1 part of dispersant admitted. The mixture is at 20-25 ° C

309826/1069 ■ BAD ORfQlNAt

and stirred at a pH of 5 * 5 to 6.5 for 3 hours and then filtered. The dye is obtained by salting out with 25> (C- / V) sodium chloride and sanded by filtration and dried ^{at AO 0 C in vacuo.} If it is applied to cellulose fibers together with an acid-binding agent, it dyes the fibers in bright bluish-red shades with good fastness properties.

The following table describes further dye examples which were prepared in a manner similar to Example 79

be obtained when using a compound of the formula (2),

1 2 where the two Ys stand for -0- and R, R and η the in have the meanings given in columns II, III and IV, treated with chlorosulfonic acid and when you get the Reacts sulfonic chloride with the amine indicated in column V.

309826/1089

E.g. ^R 1 R ₂ η. Amine Hue on
cellulose 80 CH _x CH ₀ - CH _x CH ₂ - . O - 5- (ß-sulfatoethylsulfonyl) aniline bluish-red 81 ir Il O 2-methoxy-5- (ß-sulfatoethylsulfonyl) -
aniline M. 82 Il Il O 2-methoxy-5-raethyl-4- (ß-sulfato
ethyl sulfonyl) aniline ■ Il 83 It H 1 yellowish red 309826 85 It
It Il
Il 1
1 Il Il
ti - » 86 Il It 1 2-methoxy-5- (ß-sulfate ethylsulfonyl) -
aniline
3- (ß ~ sulfatoethylsulfonyl) aniline Il 690 87
88 CH _x
CH ₅ CH ₂ - CH _x
H ο
ο. 4-Cβ-sulfatoethylsulfonyl) aniline bluish-red
yellowish red 89 CH _x Il ' ,1 M.
3- (ß-sulfatoethylsulfonyl) aniline Il 90 CH _x CHpCHp- Il 1. It It 91 CH _x CH ₀ CHpCHp- It, 1 Il It M.

co GO

E.g. R ₁ R ₂ η Ainin Hue on
cellulose 92 -OH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - 0 4- (S-sulfatoethylsulfonyl) aniline bluish-red 95 -CH ₂ CII ₂ CH ₂ CH ₂ - 0 Il M. 94 -CH ₂ -CH ₂ -O-CH ₂ CH ₂ - 0 M. yellowish red 95 -Cn ₂ CH ₂ -SO ₂ -CH ₂ CH ₂ - 0 3- (B-sulfatoethylsulfonyl) aniline It 96
9? C ₂ H ₅ C ₂ H ₅
H CH ₅ 0
0 2- (ß-Aminoäthylamino) -4-chloro-6-m-
sulfoanilino) -2-s-triazine
2- (4-amino-3'-sulfoanilino) -4-ChIoPO-G-
(m-sulfoanilino) -s-triazine bluish-red

Cn ι

O W W

ro

OI O

Claims (1)

Claims wherein R is hydrogen or an alkyl group and ρ
R is an alkyl, aryl, or substituted aryl group \ 2
or in which R and R together with the IT atom form a 5- or 6-membered heterocyclic ring, η each independently represents 0 or 1, Y each independently represents hydrogen or a methyl group, or the two Y together represent an oxygen atom stand, X ~ stands for SO-, "or for CO, can,
stand / provided the two Y stand for -0-, Am stands for the group ITH or an amine or diamine radical, wherein the SOp group is bonded to the nitrogen atom or to one of the two nitrogen atoms; and Z is a cellulose reactive group "attached to a carbon or nitrogen atom in the Am radical." 3 09826/1069 2. Dyes according to claim 1, characterized marked 1 2
net, da3 R and / or R f Carbon atoms. 1 2
net, da3 R and / or R for an alkyl group with 1 to 4- 3- dyes according to claim 1 or 2, characterized in that that Z is a 2-3ulfatoäthylsulfongruppe stands. 4. Dyes according to claim 1 or 2, cb characterized by that Z is a heterocyclisch.es radical with 2 or 3 nitrogen atoms in the heterocyclic ring and with at least one cellulose reactive substituent is on a carbon atom of the ring. 5. Dyes according to claim 4, characterized in that the heterocyclic ring has an s-triazine ring is at least one chlorine atom. 6. Process for the preparation of the dyes according to Claim 1, characterized in that one is a compound the formula (6) 1 ? - wherein the symbols R, R, X, Y and η are those in claim 1 st have given meanings and Am 'for "' - 'ΪΓΗ— ■ or is the r & dical of a diamine, with an anhydride or 309826/1069 BAD ORlQtNAt a halide, an acid of which the acid radical is one Contains substituents that lead to a chemical reaction mit.der fiber with the formation of a chemical bond capable of, or with a heterocyclic compound that has a halogen atom on a carbon atom of the heterocyclic Contains bound to the core and also one of the above having reactive substituents. 7 · Process for the preparation of the dyes according to claim 1 before in Am for the radical of an amine or ■ Diamine stands, characterized in that there is a connection the formula (11) 30., Cl with an amine or diainine of the formula ■ H - Am - Z ' . (12) 1 2 - ■ converts, where the symbols R, R, X, Y, Z, Am and η die The meanings given in claim 1 have. £. A process for the preparation of the dyes according to claim 1, wherein the cellulose reactive group Z is a 0 9 8-26 / 1.069 BAD LOCATION s-triazine nucleus is formed by a chlorine or bromine atom and an amino or substituted amino group is, characterized in that a dye according to claim 1, in which Z is a dichlorocro or dibromostriazine group is, reacts with ammonia or an amine. 9 · Process for the preparation of the dyes according to claim 1, .vorin the cellulose-reactive group Z is an s-triazine nucleus which is formed by SC ₇ H, a quaternary ammonium group or a group of the formula. (2), (3) and (4) is substituted, characterized in that a dye according to claim 1, in which Z is an s-triazine group which is substituted by at least one chlorine atom, with an alkali metal salt of sch ' . \ ^r efeliger acid, a tertiary amine or a compound of the formulas (8), (9) and (10), where Y stands for a group of atoms which is necessary for the formation of a 5- or 6-membered heterocyclic ring , which may contain substituents or form part of a single system, R and R each stand for identical or different alkyl, cycloalkyl, aryl or aralkyl groups, or R ^y and R together with the nitrogen atom form a 5- or 6-membered heterocyclic ring and R 1 and R 4 may be the same or different and each represent a hydrogen atom or an alkyl, aryl or aralkyl group. 1C. Use of the dyes according to one of the claims 1 to 5 together with a treatment with an acid-binding smock for dyeing or printing textile material! en. Y ' 309826/1069 WHEEL ORIGINAL